JPH09278850A - Liquid curable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a liq. curable resin compsn. which has good storage stability and, when cured, has a good surface sliding property and is suitable as a coating agent for an optical fiber, especially as a tape material and a bundling material by using a compsn. comprising a specific polydimethylsiloxane compd.

SOLUTION: This liq. curable resin compsn. comprises a polydimethylsiloxane compd. having in one molecule at least two urethane bonds, a nonreactive org. group in its at least one terminal, and a (meth)acryloyl group in its at least one terminal.

COPYRIGHT: (C)1997,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid curable resin composition having excellent surface slipperiness of a cured product. More specifically, the present invention relates to a liquid curable resin composition suitable as a coating material for an optical fiber tape core wire or the like.

[0002]

2. Description of the Related Art In the production of an optical fiber, a resin coating is applied immediately after hot-melt spinning of a glass fiber for protection and reinforcement. As this resin coating, a structure is known in which a flexible primary coating layer is first provided on the surface of a glass fiber, and a secondary coating layer having higher rigidity is provided outside the primary coating layer. In addition, in order to put these resin-coated optical fiber strands into practical use, a so-called optical fiber in which several, for example, four or eight, are arranged on a plane and fixed with a binding material to form a rectangular tape-shaped structure. It is known to make fiber tape cores. Then, the resin composition for forming the primary coating layer is a soft material, the resin composition for forming the secondary coating layer is a hard material, and the optical fiber is bundled to form a tape core. Is called a tape material. Further, a structure in which a tape core wire is further bound to form a multi-core tape is also known, and a binding material for this purpose is called a bundling material.

A curable resin used as a coating material for such an optical fiber must be liquid at room temperature and exhibit low viscosity with excellent coatability; the liquid material has good storage stability and composition distribution. Not hardening; fast curing and good productivity; sufficient strength and flexibility; little change in physical properties with a wide range of temperature changes; heat resistance;
Excellent hydrolysis resistance; little change in physical properties over time; long-term reliability; excellent resistance to chemicals such as acids and alkalis; low moisture absorption and water absorption; light resistance The following properties are required: excellent oil resistance; excellent oil resistance; low generation of hydrogen gas that adversely affects the optical fiber; and good surface slippage of the cured product.

Further, in the production of optical fiber tape cores and multi-core tapes, in order to produce optical fiber cables smoothly in the next step, the produced tape cores can be smoothly wound and wound. It is important that the tape core can be pulled out smoothly at a constant speed.
Conventionally, a lubricant such as silicone oil or a powder such as talc has been applied to the surface of the tape core wire to impart surface slipperiness to the tape core wire, so that winding and drawing can be smoothly performed.

There is also known a method in which an additive such as silicone oil is added to a tape material or a bundling material to impart a surface slip property to a tape core wire. However, in the case of the conventional additives, although a large amount of the additive improves the surface slipperiness of the cured product, the liquid composition is separated into two phases during storage, and there is a problem in storage stability. On the other hand, if the addition amount is small, the storage stability is good, but sufficient surface slippage cannot be imparted, and powder such as talc has to be applied at the time of tape core production.

[0006]

For tape materials and bundling materials, it is strongly desired to manufacture a tape core wire without applying a lubricant such as silicone oil or powder such as talc to the surface of the tape core wire. However, one of the important required properties is that the cured product has good surface slipperiness.

Further, when an additive is added to the liquid curable resin composition for the purpose of imparting surface slipperiness, liquid-liquid separation should not occur, and the liquid curable resin composition should not be separated even after long-term storage. The composition must be uniform and the properties of the cured product must be the same as during production.

Therefore, the present invention has good storage stability,
Further, it is an object of the present invention to provide a liquid curable resin composition which is suitable as a coating material for optical fibers, particularly a tape material and a bundling material, which has good surface slipperiness of a cured product.

[0009]

According to the present invention, the above objects and advantages of the present invention are as follows: (i) at least two urethane bonds and (ii) at least one terminal are non-reactive in one molecule. And a liquid curable resin composition containing a polydimethylsiloxane compound having (iii) an organic group having a (meth) acryloyl group at at least one terminal. In the present invention, the polydimethylsiloxane compound has at least two urethane bonds and has a (meth) acryloyl group at at least one terminal, as described above.
At least two urethane bonds are necessary to improve the compatibility between the polydimethylsiloxane compound and other components and to enhance the storage stability of the liquid curable resin composition.

The urethane bond is a polyisocyanate,
It is formed by reacting a reactive silicone compound having a hydroxyl group at at least one terminal, which will be described later, and a hydroxyl group-containing (meth) acrylate.

Polyisocyanates suitable for this purpose are:
Examples of the diisocyanate include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate,
3-xylylene diisocyanate, 1,4-xylylene diisocyanate, 1,5-naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 4,4 ' -Diphenylmethane diisocyanate, 3,3'-dimethylphenylene diisocyanate, 4,4'-biphenylene diisocyanate, 1,6-hexane diisocyanate, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate), 2,2,4-trimethylhexamethylene diisocyanate , Bis (2-isocyanatoethyl) fumarate, 6-isopropyl-1,3-phenyl diisocyanate, 4-diphenylpropane diisocyanate, lysine diisocyanate , Hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, tetramethyl xylylene diisocyanate, 2,
5 (or 6) -bis (isocyanatomethyl) -bicyclo [2.2.1] heptane and the like. Among these, in particular, 2,4-tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate,
Methylene bis (4-cyclohexyl isocyanate) and the like are preferred. These are used alone or in combination of two or more.

The polydimethylsiloxane structure in the polydimethylsiloxane compound used in the present invention is introduced by using a silicone compound having a hydroxyl group at at least one terminal and a non-reactive organic group at at least one terminal. It As such a silicone compound,
At one end, for example, 3- (2'-hydroxyethoxy) propyl group, 3- (2 ', 3'-dihydroxypropyloxy) propyl group, 3- (2'-ethyl-2'-
Hydroxymethyl-3-hydroxy) propyl group and 3- (2'-hydroxy-3'-isopropylamino)
Examples thereof include silicone compounds having a hydroxyl group at one end, such as polydimethylsiloxane having an organic group such as a propyl group and a non-reactive organic group such as a trimethylsilyloxy group at the other end. These are used alone or in combination of two or more.

The silicone compound having a hydroxyl group at one end as described above is, for example, Silaplane FM-041.
1, FM-0421, FM-0425, FM-D41
1, FM-D421, FM-D425 (above, manufactured by Chisso Corporation), TSL9105 (Toshiba Silicone Corporation)
Shin-Etsu Silicones X-22-170A, X-22
170B, X-22-170D, X-22-176B,
X-22-176D, X-22-176DX, X-22
-178A and X-22-178B (all manufactured by Shin-Etsu Chemical Co., Ltd.).

The (meth) acryloyl group is necessary for imparting radiation curability to the polydimethylsiloxane compound used in the present invention. This (meth) acryloyl group is introduced by reacting a hydroxyl group-containing (meth) acrylate with polyisocyanate.

Examples of such a hydroxyl group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate,
-Hydroxy-3-phenyloxypropyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate, 2-hydroxyalkyl (meth) acryloyl phosphate, 4-hydroxycyclohexyl (meth) acrylate, 1,6-hexane Diol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, trimethylolpropane di (meth)
Acrylate, trimethylolethane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, the following formula (1) or (2) CH ₂ = C (R ¹ ) -COOCH ₂ CH ₂ -(OCOCH ₂ CH ₂ CH ₂ CH ₂ CH ₂ ) n-OH CH ₂ = C (R ¹ ) -COOCH ₂ CH (OH) CH ₂ -O- (C ₆ H ₅ ) (In the formula, R ¹ is hydrogen. Represents an atom or a methyl group, n is 1
(Indicating the number of 1 to 15). Further, a compound obtained by addition reaction of a glycidyl group-containing compound such as alkyl glycidyl ether, allyl glycidyl ether, glycidyl (meth) acrylate and (meth) acrylic acid can also be used. Among these hydroxyl group-containing (meth) acrylates, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and the like are particularly preferable. These are used alone or in combination of two or more.

As the reaction for obtaining the polydimethylsiloxane compound, for example, a method in which a silicone compound having a hydroxyl group, a polyisocyanate and a hydroxyl group-containing (meth) acrylate are charged all at once and reacted, the silicone compound and the polyisocyanate are reacted And then reacting with a hydroxyl group-containing (meth) acrylate; polyisocyanate and hydroxyl group-containing (meth) acrylate
Examples thereof include a method of reacting an acrylate and then a reaction of the silicone compound. The reaction is preferably performed such that the hydroxyl group equivalent of the silicone compound having a hydroxyl group and the hydroxyl group-containing (meth) acrylate and the isocyanate equivalent of the polyisocyanate substantially match.

Further, by adding a polyol to the starting material of the above reaction, a structure such as polyurethane polyol can be introduced between the polydimethylsiloxane structure and the (meth) acryloyl group.

As the polyol used here, polyether diol, polyester diol, polycarbonate diol, polycaprolactone diol and the like are used, and these polyols can be used in combination of two or more kinds. The bonding mode of the structural units in these polyols is not particularly limited, and may be any of a random bond, a block bond, and a graft bond.

Specific examples of the polyether diol include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyhexamethylene glycol, polyheptamethylene glycol,
Examples include polydecamethylene glycol or polyether diol obtained by ring-opening copolymerization of two or more ion-polymerizable cyclic compounds. Examples of the ion-polymerizable cyclic compound include ethylene oxide, propylene oxide, butene-1-oxide, isobutene oxide,
3,3-bischloromethyloxetane, tetrahydrofuran, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran, dioxane, trioxane, tetraoxane, cyclohexene oxide, styrene oxide,
Cyclic ethers such as epichlorohydrin, glycidyl methacrylate, allyl glycidyl ether, allyl glycidyl carbonate, butadiene monoxide, isoprene monoxide, vinyl oxetane, vinyl tetrahydrofuran, vinyl cyclohexene oxide, phenyl glycidyl ether, butyl glycidyl ether, and glycidyl benzoate; Can be Specific combinations of the two or more ion-polymerizable cyclic compounds include, for example, tetrahydrofuran and propylene oxide, tetrahydrofuran and 2-methyltetrahydrofuran, tetrahydrofuran and 3-methyltetrahydrofuran, tetrahydrofuran and ethylene oxide, propylene oxide and ethylene oxide, butene-1 -Oxide and ethylene oxide, tetrahydrofuran and butene-1
Examples thereof include a terpolymer of oxide and ethylene oxide. Further, a polyether diol obtained by ring-opening copolymerization of the above-mentioned ion-polymerizable cyclic compound and cyclic imine such as ethyleneimine; cyclic lactone acid such as β-propiolactone and glycolic acid lactide; or dimethylcyclopolysiloxane. Can also be used. The ring-opening copolymers of these ionic polymerizable cyclic compounds may be randomly bonded or may be in a block-like bond.

Examples of polyester diols include polyester diols obtained by reacting a polyhydric alcohol with a polybasic acid. Examples of the polyhydric alcohol include ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, tetramethylene glycol, polytetramethylene glycol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol and 3-
Examples thereof include methyl-1,5-pentanediol, 1,9-nonanediol, and 2-methyl-1,8-octanediol. Examples of the polybasic acid include phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, adipic acid, sebacic acid and the like. These polyester diols include Clapol P-2010, PMIPA,
PKA-A, PKA-A2, PNA-2000 (or more,
(Kuraray Co., Ltd.).

Examples of the polycarbonate diols include polytetrahydrofuran polycarbonate and 1,6-hexanediol polycarbonate. Commercially available products are DN-980, 981, 9
82, 983 (all made by Nippon Polyurethane Co., Ltd.), P
C-8000 (manufactured by PPG, USA), PC-THF-
It can be obtained as a CD (manufactured by BASF) or the like.

Further, examples of the polycaprolactone diol include polycaprolactone diol obtained by reacting ε-caprolactone with a diol. Examples of the diol include ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, tetramethylene glycol, polytetramethylene glycol, 1,2-polybutylene glycol, 1,6-hexanediol, neopentyl glycol, and 1,4-glycol. Cyclohexanedimethanol, 1,4-butanediol, and the like. These polycaprolactone diols are available in Praxel 205, 205AL, 21
2,212AL, 220, 220AL (all manufactured by Daicel Corporation) and the like can be obtained as commercial products.

Examples of polyols other than the above include ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, Hydrogenated bisphenol A, hydrogenated bisphenol F, dimethylol compound of dicyclopentadiene, tricyclodecane dimethanol, pentacyclopentadecane dimethanol, β-methyl-δ-valerolactone, hydroxy-terminated polybutadiene, hydroxy-terminated hydrogenated polybutadiene, castor oil Examples thereof include modified polyols, polydimethylsiloxane terminal diol compounds, and polydimethylsiloxane carbitol modified polyols. The preferred molecular weight of the polyol is usually from 50 to 15,000, particularly preferably from 100 to 8,000, as the number average molecular weight in terms of polystyrene.

As a reaction for obtaining a polydimethylsiloxane compound having a polyol structure, for example, a silicone compound having a hydroxyl group, a polyol, a polyisocyanate and a hydroxyl group-containing (meth) acrylate are charged all at once and reacted. A method of reacting an isocyanate and then reacting the silicone compound and a hydroxyl group-containing (meth) acrylate;
Method of reacting polyisocyanate, the above silicone compound and hydroxyl group-containing (meth) acrylate and then reacting with a polyol; reacting polyisocyanate and the above silicone compound, then reacting with a polyol, and finally reacting with a hydroxyl group containing (meth) acrylate A method of reacting; polyisocyanate and a hydroxyl group-containing (meth) acrylate are reacted, then a polyol is reacted, and finally the above-mentioned silicone compound is reacted.

The urethane bond in the polydimethylsiloxane compound used in the present invention is introduced into only one end of the polydimethylsiloxane structure as described above. If urethane bonds are introduced at all terminals of the polydimethylsiloxane structure, sufficient surface slip properties cannot be obtained.

The polystyrene-equivalent number average molecular weight of the polydimethylsiloxane compound used in the present invention is from 800 to
It is preferably 15,000, particularly 1000 to 7
A range of 000 is preferred. If the number average molecular weight is less than 800, the cured product of the composition containing the same may not have sufficient surface slipperiness. If the number average molecular weight exceeds 15,000, the composition containing the same may have a liquid storage stability. May be inferior.

The polydimethylsiloxane compound used in the present invention is contained in the liquid curable composition in an amount of 0.05 to 1
It is preferably contained in an amount of 0% by weight, particularly 0.1 to 7
A range of weight% is preferred. If the content of the polydimethylsiloxane compound is less than 0.05% by weight, the surface slipperiness of the cured product may be insufficient, and if it exceeds 10% by weight, the liquid storage stability may be poor.

The liquid curable resin composition of the present invention can contain a urethane (meth) acrylate obtained by the reaction of a polyol, a diisocyanate and a hydroxyl group-containing (meth) acrylate.

These urethane (meth) acrylates are
It is produced by reacting the isocyanate group of the diisocyanate with the hydroxyl group of the polyol and the hydroxyl group of the hydroxyl group-containing (meth) acrylate, respectively.

As this reaction, for example, a method of charging a polyol, a diisocyanate and a hydroxyl group-containing (meth) acrylate all at once and reacting them; reacting the polyol and the diisocyanate and then reacting with a hydroxyl group (meth)
A method of reacting an acrylate; a method of reacting a diisocyanate and a hydroxyl group-containing (meth) acrylate, followed by a reaction of a polyol; a method of reacting a diisocyanate and a hydroxyl group-containing (meth) acrylate, then reacting the polyol, and finally reacting the hydroxyl group-containing (meth) ) A method of reacting an acrylate.

As the polyol diisocyanate and the hydroxyl group-containing (meth) acrylate used here, the above-mentioned compounds can be used.

The proportion of the polyol, diisocyanate and hydroxyl group-containing (meth) acrylate used is such that the isocyanate group contained in the diisocyanate is 1.1 to 3 equivalents per 1 equivalent of the hydroxyl group contained in the polyol, and the hydroxyl group of the hydroxyl group-containing (meth) acrylate is used. Is preferably 0.2 to 1.5 equivalents, and it is particularly preferable that the equivalent of the hydroxyl group in the polyol and the acrylate and the equivalent of the isocyanate group in the diisocyanate are substantially equal.

In the reaction of these compounds, copper naphthenate, cobalt naphthenate, zinc naphthenate, di-n-butyltin laurate, triethylamine, 1,4 are usually used.
A urethanization catalyst such as diazabicyclo [2.2.2] octane, 2,6,7-trimethyl-1,4-diazabicyclo [2.2.2] octane is used in an amount of 0 based on 100 parts by weight of the total amount of the reactants. It is preferable to use 0.01 to 1 part by weight. Also,
The reaction temperature is usually 10 to 90 ° C., preferably 30 to 80 ° C.

Urethane (meta) thus obtained
The acrylate is preferably incorporated in the entire composition in an amount of 0 to 90% by weight. Particularly, the coatability when coating the optical fiber core wire, the tensile breaking strength, the tensile elongation at break of the coating material after curing, and To maintain long-term reliability,
It is preferable to mix 70% by weight.

The liquid curable resin composition of the present invention may further contain a urethane (meth) acrylate obtained by reacting 2 moles of a hydroxyl group-containing (meth) acrylate compound with 1 mole of diisocyanate. Examples of the urethane (meth) acrylate include a reaction product of hydroxyethyl (meth) acrylate and 2,5 (or 2,6) -bis (isocyanatomethyl) -bicyclo [2.2.1] heptane, and hydroxyethyl (meth) acrylate. A) a reaction product of acrylate and 2,4-tolylene diisocyanate, a reaction product of hydroxyethyl (meth) acrylate and isophorone diisocyanate, a reaction product of hydroxypropyl (meth) acrylate and 2,4-tolylene diisocyanate, And a) a reaction product of acrylate and isophorone diisocyanate.

To the liquid curable resin composition of the present invention, a polymerizable monomer having a vinyl group or a (meth) acryloyl group can be added together with the above urethane (meth) acrylate. Such polymerizable monomers include monofunctional monomers and polyfunctional monomers, and examples of monofunctional monomers include N-vinylpyrrolidone and N-
Vinyl group-containing monomers such as vinylcaprolactam, vinylimidazole, and vinylpyridine; isobornyl (meth) acrylate, bornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) ) Acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, acryloylmorpholine, 2-hydroxyethyl (meth) acrylate, 2-
Hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, amyl (meth) Acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) Acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate Dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, butoxyethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, benzyl (meth) )
Acrylate, phenoxyethyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, methoxyethylene glycol (meth) acrylate, ethoxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene Glycol (meth) acrylate, diacetone (meth) acrylamide, isobutoxymethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, t-octyl (meth) acrylamide,
Dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 7-amino-3,
7-dimethyloctyl (meth) acrylate, N, N-
Diethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, hydroxybutyl vinyl ether, lauryl vinyl ether, cetyl vinyl ether, 2-ethylhexyl vinyl ether and the following formulas (3) to (5) CH ₂ = C (R ² ). ^{-COO (R 3 O) mR 4} ( wherein, R ² represents a hydrogen atom or a methyl group, R ³ is 2 to 6 carbon atoms, preferably an alkylene group having from 2 to 4,
R ⁴ is a hydrogen atom or a carbon number of 1 to 12, preferably 1 to
9 represents an alkyl group, and m is 0 to 12, preferably 1 to
8 is shown)

[0037]

Embedded image

[0038] (wherein, R ² are as defined above, R ⁵
Represents an alkylene group having 2 to 8, preferably 2 to 5 carbon atoms, and p represents a number of 1 to 8, preferably 1 to 4)

[0039]

Embedded image

(Wherein, R ² , R ⁵ and p have the same meaning as described above, and R ⁶ represents a hydrogen atom or a methyl group), and a (meth) acryloyl group-containing monomer represented by the formula: As commercial products, Aronix M111, M
113, M114, M117 (above, Toa Gosei Co., Ltd.)
Manufactured); KAYARADTC110S, R629, R64
4 (above, manufactured by Nippon Kayaku Co., Ltd.); Viscoat 3700
(Made by Osaka Organic Chemistry) and the like.

Examples of the polyfunctional monomer include, for example, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di ( (Meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropanetrioxyethyl (meth) acrylate, tris ( 2-hydroxyethyl) isocyanurate tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, tricyclodecanediyldimethyldi (meth) acrylate To di (meth) acrylates of diols of ethylene oxide or propylene oxide adducts of bisphenol A, di (meth) acrylates of diols of ethylene oxide or propylene oxide adducts of hydrogenated bisphenol A, and diglycidyl ethers of bisphenol A Epoxy (meth) acrylate to which (meth) acrylate is added, diacrylate of polyoxyalkylenated bisphenol A, and (meth) acryloyl group-containing monomers such as triethylene glycol divinyl ether are exemplified. Commercially available products include, for example, Iupimer UV SA1002, SA20
07 (above, Mitsubishi Yuka); Viscoat 700 (Osaka Organic Chemicals); KAYARAD R-604, DPCA-
20, -30, -60, -120, HX-620, D-
310, D-330 (all manufactured by Nippon Kayaku); Aronix M-210, M-215, M-315, M-325
(Above, manufactured by Toagosei Kagaku) and the like. Of these, tricyclodecanediyldimethyl diacrylate and polyoxyalkylenated bisphenol A diacrylate are particularly preferred.

These polymerizable monomers constitute 8
It is preferable to add 0% by weight or less, particularly 20 to 70% by weight. If it exceeds 80% by weight, the curing speed may be low, which is not preferable.

The liquid curable resin composition of the present invention is cured by heat and / or radiation. Here, radiation means infrared rays, visible rays, ultraviolet rays, X-rays, electron beams, α rays,
Beta rays, γ rays, etc.

A polymerization initiator may be added to the liquid curable resin composition of the present invention. As the polymerization initiator, a thermal polymerization initiator or a photopolymerization initiator can be used.

When the liquid curable resin composition of the present invention is heat-cured, a thermal polymerization initiator such as a peroxide or an azo compound is usually used. Specific examples include benzoyl peroxide, t-butyl-oxybenzoate, and azobisisobutyronitrile.

When the liquid curable resin composition of the present invention is cured by radiation, a photopolymerization initiator is used, and if necessary, a photosensitizer is added. Here, as the photopolymerization initiator, for example, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-
Phenylacetophenone, xanthone, fluorenone,
Benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, Michler's ketone, benzoinpropyl ether, benzoin ethyl ether, benzyldimethyl Ketal,
1- (4-isopropylphenyl) -2-hydroxy-
2-methylpropan-1-one, 2-hydroxy-2-
Methyl-1-phenylpropan-1-one, thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2-methyl-
1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis- (2,6
-Dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide; IRGACURE184,
369, 651, 500, 907, CGI1700, C
GI1750, CGI1850, CG24-61 (above, manufactured by Ciba Geigy); Lucirin LR8728
(Manufactured by BASF); Darocur 1116, 1173
(Above, manufactured by Merck); Yubecryl P36 (manufactured by UCB) and the like. Examples of the photosensitizer include triethylamine, diethylamine, N-methyldiethanolamine, ethanolamine, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, and 4-dimethylaminobenzoate. Isoamyl acid; Yubecryl P102, 103, 104, 10
5 (above, made by UCB) and the like.

When the liquid curable resin composition of the present invention is cured by using heat and radiation in combination, the thermal polymerization initiator and the photopolymerization initiator may be used in combination. It is preferable that the polymerization initiator is incorporated in the total composition in an amount of 0.1 to 10% by weight, particularly 0.5 to 7% by weight.

In the liquid curable resin composition of the present invention, in addition to the above components, other curable oligomers or polymers may be added, if necessary, within the range not impairing the properties of the liquid curable resin composition of the present invention. It can be blended.

Examples of the other curable oligomers or polymers include polyester (meth) acrylate, epoxy (meth) acrylate, polyamide (meth) acrylate, siloxane polymer having a (meth) acryloyloxy group, and glycidyl methacrylate. Examples thereof include a reactive polymer obtained by reacting a copolymer with another polymerizable monomer and (meth) acrylic acid.

Further, the liquid curable resin composition of the present invention can be used in combination with a diamine in order to suppress generation of hydrogen gas which causes transmission loss of the optical fiber. As such a diamine, Ethylenediamine,
Examples thereof include diamines such as tetramethylenediamine, hexamethylenediamine, paraphenylenediamine, 4,4′-diaminodiphenylmethane, diamines containing a hetero atom, and polyetherdiamines.

In addition to the above components, various additives such as antioxidants, ultraviolet absorbers, light stabilizers, silane coupling agents, coating surface improving agents, thermal polymerization inhibitors, leveling agents, surfactants, colorants. , Storage stabilizer, plasticizer, lubricant, solvent,
Fillers, antioxidants, wetting improvers, and the like can be added as necessary. Here, as the antioxidant,
For example, Irganox 1010, 1035, 1076,
1222 (all made by Ciba-Geigy), Antigen
P, 3C, FR, GA-80 (manufactured by Sumitomo Chemical Co., Ltd.)
And the like; examples of the ultraviolet absorber include Tinu
vin P, 234, 320, 326, 327, 32
8, 329, 213 (above, made by Ciba Geigy), See
sorb102, 103, 110, 501, 202, 7
12, 704 (above, manufactured by Cypro Kasei Co., Ltd.) and the like; examples of the light stabilizer include Tinuvin 29
2,144,622LD (above, manufactured by Ciba Geigy), Sanol LS770 (manufactured by Sankyo Co., Ltd.), Sumisorb
TM-061 (produced by Sumitomo Chemical Co., Ltd.) and the like; examples of the silane coupling agent include γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, and γ-methacryloxypropyltrimethoxysilane. , As commercially available products, SH6062, 60
30 (above, manufactured by Toray Silicone Co., Ltd.), KBE90
3, 603, 403 (all manufactured by Shin-Etsu Chemical Co., Ltd.) and the like; examples of the coating surface improver include silicone additives such as dimethyl siloxane polyether.
As commercial products, DC-57, DC-190 (above, manufactured by Dow Corning), SH-28PA, SH-29PA, S
H-30PA, SH-190 (all manufactured by Toray Dow Corning), KF351, KF352, KF353, KF
354 (above, Shin-Etsu Chemical Co., Ltd.), L-700,
L-7002, L-7500, FK-024-90 (above, Nippon Unicar Co., Ltd. make) etc. are mentioned.

The viscosity of the liquid curable resin composition of the present invention is
Usually 200 to 20000 cp / 25 ° C, especially 2000 to 2000
15000 cp / 25 ° C. is preferred. When the liquid curable resin composition of the present invention is used as a tape material or a bundling material, the Young's modulus after curing is 10 to 25.
0 kg / mm ^2, preferably Of particular 40~150kg / mm ^2.

Further, the surface slip property is 0.1 to 1.5 kg /
cm ² , particularly preferably 0.1 to 1.0 kg / cm ² . If the surface slipperiness exceeds 1.5 kg / cm ² , the tape core wire cannot be pulled out at a constant speed during the production of the optical fiber cable. On the other hand, if it is less than 0.1 kg / cm ² , the surface is too slippery during the production of the tape core wire, and it cannot be wound up regularly.

[0054]

EXAMPLES The present invention will be described below in more detail with reference to examples, but the present invention is not limited to these examples. In the following, “parts” means “parts by weight”.

Synthesis Example 1 of polydimethylsiloxane compound In a reaction vessel equipped with a stirrer, 2.8 parts of tolylene diisocyanate, α- [3- (2'-hydroxyethoxy) propyl] having a hydroxyl equivalent of 6,000, ω- Trimethylsilyloxypolydimethylsiloxane 95.4 parts and a polymerization inhibitor 2,6-di-t-butyl-p-cresol.
02 parts were prepared. Then, these were cooled with ice until the liquid temperature became 10 ° C. or lower while stirring them. When the liquid temperature reached 10 ° C or lower, 0.08 part of dibutyltin dilaurate was added, and the mixture was stirred for 1 hour while controlling the liquid temperature at 20 to 30 ° C, and then stirred at 40 to 50 ° C for 2 hours. Then, 1.8 parts of hydroxyethyl acrylate was added, and the liquid temperature was 50 to 6
Stirring was continued at 0 ° C. for 3 hours, and the reaction was terminated when the residual isocyanate content was 0.1% by weight or less. The number average molecular weight of the obtained polydimethylsiloxane compound (the polystyrene equivalent number average molecular weight was measured by gel permeation chromatography using AS-8020 manufactured by Tosoh Corporation. The same applies hereinafter) was 6,100. The resin liquid of the polydimethylsiloxane compound obtained by this method is designated as SA-1.

Synthesis Example 2 of Polydimethylsiloxane Compound In a reaction vessel equipped with a stirrer, 16.6 parts of isophorone diisocyanate, 0.08 part of dibutyltin dilaurate and 0.02 part of 2,6-di-t-butyl-p-cresol. Was charged and cooled to 15 ° C. or lower. Temperature is 3 while stirring
8.7 parts of hydroxyethyl acrylate was added dropwise so as to keep the temperature below 0 ° C. After the dropping was completed, the reaction was carried out at 30 ° C. for 1 hour. Next, α- [3-
(2′-Hydroxyethoxy) propyl] and 74.7 parts of ω-trimethylsilyloxypolydimethylsiloxane were added and stirred at 20 to 55 ° C. The reaction was terminated when the residual isocyanate became 0.1% by weight or less. The number average molecular weight of the obtained polydimethylsiloxane compound is 1
400. The resin solution of the polydimethylsiloxane compound obtained by this method is referred to as SA-2.

Synthesis Example 3 of polydimethylsiloxane compound In a reaction vessel equipped with a stirrer, 15.3 parts of tolylene diisocyanate and α- [3- (2 ', 3') having a hydroxyl equivalent of 850.
-Dihydroxypropyloxy) propyl] -ω-trimethylsilyloxypolydimethylsiloxane 74.6 parts and 2,6-di-t-butyl-p-cresol 0.02
The department was charged. Then, while stirring these, the liquid temperature becomes 1
The mixture was cooled on ice until the temperature reached 0 ° C or lower. When the liquid temperature became 10 ° C or lower, 0.08 part of dibutyltin dilaurate was added, and the mixture was stirred for 1 hour while controlling the liquid temperature at 20 to 30 ° C.
It stirred at 40-50 degreeC for 2 hours. Then, 10.2 parts of hydroxyethyl acrylate was added thereto, and the liquid temperature was 50-
The stirring was continued at 60 ° C. for 3 hours, and the reaction was terminated when the residual isocyanate content was 0.1% by weight or less. The number average molecular weight of the obtained polydimethylsiloxane compound is 1
800. The resin solution of the polydimethylsiloxane compound obtained by this method is designated as SA-3.

Synthesis Example 4 of polydimethylsiloxane compound In a reaction vessel equipped with a stirrer, 6.2 parts of tolylene diisocyanate and α- [3- (2 ', 3') having a hydroxyl equivalent of 2500.
-Hydroxypropyloxy) propyl]-[omega] -trimethylsilyloxypolydimethylsiloxane 89.6 parts and 2,6-di-t-butyl-p-cresol 0.02 parts were charged. Then, while stirring these, the liquid temperature becomes 10
The mixture was cooled on ice until the temperature fell to below ° C. When the liquid temperature became 10 ° C. or lower, 0.08 part of dibutyltin dilaurate was added, and the mixture was stirred for 1 hour and 2 hours while controlling the liquid temperature at 20 to 30 ° C. and 40 to 50 ° C., respectively. Then, 4.2 parts of hydroxyethyl acrylate was added thereto, and the liquid temperature was 50-60.
Stirring was continued for 3 hours at 0 ° C, and the reaction was terminated when the residual isocyanate content was 0.1% by weight or less. The number average molecular weight of the obtained polydimethylsiloxane compound was 52.
It was 00. The resin solution of the polydimethylsiloxane compound obtained by this method is referred to as SA-4.

Synthesis Example 5 of polydimethylsiloxane compound In a reaction vessel equipped with a stirrer, 22.8 parts of tolylene diisocyanate and a hydroxyl equivalent of α- [3- (2'-
Hydroxyethoxy) propyl] -ω-trimethylsilyloxypolydimethylsiloxane 65.5 parts and 2.6
-Di-t-butyl-p-cresol 0.02 parts was charged. Then, these were cooled with ice until the liquid temperature became 10 ° C. or lower while stirring them. When the liquid temperature falls below 10 ° C, 0.08 part of dibutyltin dilaurate is added to adjust the liquid temperature to 20 ° C.
Stir for 2 hours while controlling at ~ 30 ° C, then 40 ~ 5
Stirred at 0 ° C. for 1 hour. Then, after cooling the liquid temperature to 20 ° C. or lower, 4.1 parts of ethylene glycol was added, and the mixture was stirred for 0.5 hours while controlling the liquid temperature at 20 to 30 ° C., and then stirred at 40 to 50 ° C. for 1 hour. . After that, 7.6 parts of hydroxyethyl acrylate was added, and the liquid temperature was 50 to 6
Stirring was continued at 0 ° C. for 2 hours, and the reaction was terminated when the residual isocyanate content was 0.1% by weight or less. The number average molecular weight of the obtained polydimethylsiloxane compound was 18
It was 00. The resin solution of the polydimethylsiloxane compound obtained by this method is referred to as SA-5.

Synthesis Example 1 of Urethane Acrylate 1 Tolylene diisocyanate 1 was placed in a reaction vessel equipped with a stirrer.
Charge 4 parts, dibutyltin dilaurate 0.08 part, 2,6-di-t-butyl-p-cresol 0.02 part, N-vinylpyrrolidone 7.7 parts and tricyclodecanediyldimethyldiacrylate 15.5 parts. Cooled to 5-10 ° C. While stirring, 5.8 parts of hydroxyethyl acrylate was added dropwise so that the temperature was kept at 10 ° C. or lower. After the dropping was completed, the reaction was carried out at 30 ° C. for 1 hour. Next, 1.7 parts of ethylene glycol and 54.7 parts of polytetramethylene glycol having a number average molecular weight of 2,000 were added, and
The reaction was carried out at 50 ° C for 2 hours. Further, 0.5 part of hydroxyethyl acrylate was added, the reaction was continued at 50 to 60 ° C., and the reaction was continued until the residual isosonate became 0.1% by weight or less to obtain urethane acrylate UA-1.

Synthesis Example 2 of Urethane Acrylate In a reaction vessel equipped with a stirrer, 6.3 parts of tolylene diisosonate and 0.01 part of dibutyltin dilaurate, 2,6
-Di-t-butyl-p-cresol 0.009 parts and isobornyl acrylate 16 parts were added and cooled to 5-10 ° C. After 8.4 parts of hydroxyethyl acrylate was added dropwise so that the temperature became 40 ° C. or lower, the reaction was allowed to proceed at 45 to 55 ° C. for another hour. The reaction was terminated when the residual isocyanate became 0.1% by weight or less. 2.6 parts of N-vinylpyrrolidone, 6.8 parts of tricyclodecanediyldimethyldiacrylate, 2,2'-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenylpropyiene] Onate)] 0.3 part, UA-
56 parts of 1 and 0.1 parts of diethylamine were added, 4
The mixture was stirred at 0 to 50 ° C to obtain a uniform transparent liquid. This resin liquid is referred to as UA-2.

Comparative Synthesis Example 1 of Polydimethylsiloxane Compound Reactive with Both Terminals In a reaction vessel equipped with a stirrer, 22 parts of tolylene diisocyanate and hydroxyl equivalent 500 α, ω-bis [3- (2'-
63.3 parts of (Hydroxyethoxy) propyl] polydimethylsiloxane and 0.02 part of 2,6-di-t-butyl-p-cresol were charged. Then, these were cooled with ice until the liquid temperature became 10 ° C. or lower while stirring them. Liquid temperature is 1
When the temperature became 0 ° C or lower, 0.08 part of dibutyltin dilaurate was added, and the mixture was stirred for 1 hour while controlling the liquid temperature at 20 to 30 ° C, and then stirred at 40 to 50 ° C for 2 hours. Then, 14.7 parts of hydroxyethyl acrylate was added thereto, and stirring was continued at a liquid temperature of 50 to 60 ° C. for 3 hours, and the reaction was terminated when the residual isocyanate was 0.1% by weight or less. The number average molecular weight of the obtained polydimethylsiloxane compound was 1500. The resin solution of the polydimethylsiloxane compound obtained by this method is RA-1
And

Preparation of Liquid Curable Resin Composition Each component having the composition shown in Table 1 and Table 2 was charged into a reaction vessel equipped with a stirrer, and stirred for 3 hours while controlling the liquid temperature at 50 to 60 ° C. to cure the liquid. A resin composition was obtained.

[0064]

[Table 1]

[0065]

[Table 2]

Test Example The liquid curable resin composition shown in the above example was cured by the following method to prepare a test piece and evaluated as follows. The results are shown in Table 3.

1. Preparation of test piece: A liquid curable resin composition was applied onto a glass plate using an applicator bar having a thickness of 250 μm. This was irradiated with ultraviolet rays having an energy of 0.5 J / cm ² under nitrogen. The cured product was conditioned for 12 hours or more in an atmosphere of 23 ° C. and a humidity of 50%, and then used for preparing test pieces. Peel this cured product from the glass plate,
After cutting into a width of 3 cm, it was fixed to an aluminum plate with a double-sided tape so that the surface irradiated with ultraviolet rays became the front side. Using two test pieces, the surfaces of the cured products were overlapped with each other, sandwiched between double clips, and subjected to a surface slip test.

2. Surface slipperiness test: The surface slipperiness of the test piece was such that the pulling speed was 50 mm / min, the contact area of the surface of the cured product was 5.4 cm ² , and the pressure applied by the double clip was 0.48.
Shear slip test was conducted at kg / cm ² , and shear slip force was calculated from the load at the beginning of slip (unit: kg / cm ² ).

3. Measurement of liquid storage stability The liquid storage stability of the liquid curable resin composition is 3 at 60 ° C.
After standing for 0 days, the resin liquid was dropped on a glass plate, and the separated material on the liquid surface was visually observed.

4. Measurement of Viscosity The viscosity of the liquid curable resin composition was measured at 25 ° C. using a B-type viscometer manufactured by Tokyo Keiki.

The results are shown in Tables 3 and 4.

[0072]

[Table 3]

[0073]

[Table 4]

[0074]

Industrial Applicability The liquid curable resin composition of the present invention is particularly suitable as a coating material for an optical fiber having a good liquid storage stability and a good surface slip property of a cured product, and a wood or plastic sheet. The present invention provides a material suitable as a coating material for the above. For this reason, it is an excellent material that does not require the addition of a lubricant such as silicone oil or talc at the time of manufacturing an optical fiber tape core wire. Further, when used as a covering material for wood, plastic sheets, etc., slidability and an effect of preventing sticking between materials are expected.

The preferred embodiments of the present invention will be described below. 1. A number average molecular weight of 800 to 15, which has at least one organic group containing at least two urethane bonds and one or two (meth) acryloyl groups at the other end and is blocked at the other end by a non-reactive organic group, Liquid curable resin composition containing 0.05 to 10% by weight of polydimethylsiloxane compound. 2. The liquid curable resin composition according to 1 above, wherein the polydimethylsiloxane compound is formed by a reaction of a silicone compound having a hydroxyl group at one end, a polyisocyanate compound and a hydroxyl group-containing (meth) acrylate. 3. The liquid curable resin composition according to 1 above, wherein the polydimethylsiloxane compound is formed by a reaction of a silicone compound having a hydroxyl group at one end, a polyol compound, a polyisocyanate compound, and a hydroxyl group-containing (meth) acrylate. 4. A silicone compound having a reactive hydroxyl group at one end has a 3- (2′-hydroxyethoxy) propyl group or a 3- (2 ′, 3′-dihydroxypropyloxy) propyl group at one end, The liquid curable resin composition according to the above 2 or 3, wherein the other end is a polydimethylsiloxane compound blocked with a trimethylsilyloxy group. 5. The liquid curable resin composition according to the above 1, further containing a urethane (meth) acrylate formed by the reaction of a polyol, a diisocyanate and a hydroxyl group-containing (meth) acrylate. 6. The liquid curable resin composition as described in 6 above, which contains 90% by weight or less of urethane (meth) acrylate. 7. The liquid curable resin composition as described in 6 above, which further contains a polymerizable monofunctional or polyfunctional monomer having a (meth) acryloyl group or a vinyl group. 8. The liquid curable resin composition as described in 6 above, which contains the polymerizable monomer in an amount of 80% by weight or less.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location // G02B 6/44 301 G02B 6/44 301A 371 371 G03F 7/027 501 G03F 7/027 501 513 513 7/038 505 7/038 505 7/075 511 7/075 511 (72) Inventor Junji Yoshizawa 2-11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Co., Ltd. (72) Inventor Zen Komiya Tokyo 2-11-24 Tsukiji, Chuo-ku, Tokyo Within Japan Synthetic Rubber Co., Ltd. (72) Inventor Takashi Ukaji 2-11-24 Tsukiji, Chuo-ku, Tokyo Within Japan Synthetic Rubber Co., Ltd.

Claims (1)

[Claims] 1. In one molecule, (i) at least two urethane bonds, (ii) at least one terminal non-reactive organic group, and (iii) at least one terminal (meth).
A liquid curable resin composition comprising a polydimethylsiloxane compound having an acryloyl group.